Synthetic Routes to Ga(CN)3 and MGa(CN)4 (M = Li, Cu) Framework Structures
详细信息 查看全文
- 作者：Louis C. Brousseau ; Darrick Williams ; J. Kouvetakis ; and M. O'Keeffe
- 刊名：Journal of the American Chemical Society
- 出版年：1997
- 出版时间：July 9, 1997
- 年：1997
- 卷：119
- 期：27
- 页码：6292 - 6296
- 全文大小：249K
- 年卷期：v.119,no.27(July 9, 1997)
- ISSN：1520-5126
文摘
Ga(CN)3 has been prepared for the first time witha new method for preparation of inorganic cyanides.Pure crystalline material is formed by reaction ofCl2GaN3 with SiMe3CN viaelimination of SiMe3N3 andSiMe3Cl.Reaction of GaCl3 with SiMe3CN alsoprovides Ga(CN)3. A new convenient route toGeMe3CN and SnMe3CN isdescribed, but reactions of GaCl3 with these compoundsresult in Lewis acid-base adducts. The compositionofGa(CN)3 was confirmed by spectroscopic and elementalanalysis. Quantitative X-ray powder diffraction wasusedto refine the cubic structure, which has CN groups with orientationaldisorder in a Prussian-blue-like network structure.The symmetry is Pm
m, a =5.295(2) Å. Ga is octahedrally surrounded by on averagethree C and three N atomswith a Ga-(C,N) bond length of 2.072(2) Å, and the C-N bondlength is 1.148(1) Å. LiGa(CN)4 wasprepared byreaction of Ga(CN)3 with LiCN and was characterized byquantitative X-ray diffraction. The symmetry isP
3m, a= 5.874(2) Å, and the structure consists of LiN4and GaC4 tetrahedra linked by C-N bonds to form twointerpenetratingnetworks of the Zn(CN)2 type.CuGa(CN)4 has a similar structure witha = 5.729(5) Å, but Cu,Ga and/orC,Ndisorder cannot be ruled out.
m, a =5.295(2) Å. Ga is octahedrally surrounded by on averagethree C and three N atomswith a Ga-(C,N) bond length of 2.072(2) Å, and the C-N bondlength is 1.148(1) Å. LiGa(CN)4 wasprepared byreaction of Ga(CN)3 with LiCN and was characterized byquantitative X-ray diffraction. The symmetry isP3m, a= 5.874(2) Å, and the structure consists of LiN4and GaC4 tetrahedra linked by C-N bonds to form twointerpenetratingnetworks of the Zn(CN)2 type.CuGa(CN)4 has a similar structure witha = 5.729(5) Å, but Cu,Ga and/orC,Ndisorder cannot be ruled out.